Dyestuffs becoming green when chromed and their manufacture



Patented Apr. 27, 1943 DYESTUFFS BECOMING GREEN WHEN GHROBIED AND THEIR MANUFACTURE Achille Conzetti and Guido Schetty, Basel, Switzerland, assignors to the firm J. R. Geigy A. G.,

Basel, Switzerland No Drawing. Application May 7, 1941, Serial No. 392,388. In Switzerland June 20, 1940 7 Claims.

In the specification of the U. S. patent application Ser. No. 347,310, filed July 24, 1940, there is described a process for the manufacture of monoazo dyestuffs which yield on wool, when after-chromed, green shades of excellent fastness to fulling, of very good fastness to light and good fastness to hot pressing, consisting in that these monoazo dyestufis are made by coupling a diazotised 2-amino-l-hydroxybenzene-4-sulfonic acid being substituted in or G-position by halogen or an alkyl group with Z-aminonaphthalene- B-carboxylic acid. The coupling is advantageously performed in a medium neutral to Congo red in presence of pyridine and at a slightly raised temperature.

On further dealing with this matter, it has now been found that dyestuffs having equally good properties of fastness are obtained by using as diazo components instead of the 2-amino-1- hydroxybenzene-4-sulfonic acids substituted in 5- or 6-position by halogen or an alkyl group used in the manufacture described in the aforesaid specification 2-amino-l-hydroxybenzene-i or -5-phenylsulfone or -sulfamide derivatives which furthermore contain outside the aminophenol nucleus a group imparting solubility in Water in place of the closed sulfonic acid group in 4- or 5-position.

Accordingly there may be used as diazo components quite generally Z-aminophenol derivatives containing in 4- or 5-position the group SO2.X. In this formula X means either a phenyl sulfonic acid or phenyl carboxylic acid residue which may further contain any desired further substituents such as halogen, nitro, alkoxy or alkyl groups, or an aliphatic or aromatic amide residue which contains a group imparting solubility in water and may contain if required further substituents such as halogen, alkyl, alkoxy and nitro groups. These o'rthoaminophenols may furthermore be substituted, for example by halogen, alkyl, alkoxy or nitro groups, preferably in 5- or G-position in cases in which the $02.2! group is in e-position, or in 4- or 6- position when this group is in 5-position of the aminophenol nucleus.

As known the technical utility of dyestuffs from diazotized ortho-aminophenol sulfonic acids and 2-aminonaphthalene-3-carboxylic acid depends on the position of the sulfonic acid group. Only 1 those dyestufis containing the sulfonic acid group in 4-position and halogen or an alkyl group in 5- or 6-position ar completely free from the defect of yielding, depending on the acidity of the dyebath, quite difierent shades, which may vary from green over olive-green to yellow-green, when chromed with compounds of hexavalent chromium according to the usual methods. Dyestuffs containing nitro groups are quite useless owing to this unsatisfactory property.

The dyestuffs of the present invention, in comparison with those described in the aforesaid specification, have a still better resistance towards varying acidity of the dyebath. It is quite particularly surprising and unexpected that even the presence of a nitro group in the diazo component has no deleterious influence on the dyeing properties of the new dyestuffs.

The following examples illustrate the invention, the parts being by weight:-

EXAMPLE 1 32.9 parts of z-amino-l-hydroxybenzenephenylsulfone-( l) -su1fonic acid-(3') are dissolved in parts of water together with 4 parts of sodium hydroxide, 6.9 parts of sodium nitrite are added and the whole is introduced by drops into a mixture of ice and 30 parts of commercial hydrochloric acid. The resulting suspension of the crystallised diazo compound is brought to a reaction violet to Congo red by the addition of sodium bicarbonate and 9 parts of pyridine are added. Dissolution occurs with the production of a yellow solution which is then introduced at room temperature into a solution of 21.8 parts of the sodium salt of 2-amino-naphthalene-3-carboxylic acid in parts of water. Coupling is finished after some hours and the dyestuff, which has in part separated as a red-brown precipitate is completely precipitated by the addition of common salt, filtered and dried. There are obtained 55-60 parts of a rust-red powder soluble in concentrated sulfuric acid to a violet-red solution. It dyes wool in an acid bath yellowish-red shades which become bluish-green when after-chromed.

Dyestuffs having similar properties are obtained if 2-amino-l-hydroXybenZene-i'-chlor0- or 3-methylor 3'-methoxy-phenylsulfone-(4)- sulfonic acid-(5') is used as diazo component instead of 2-amino-l-hydroxybenzene-phenylsultone-(4) -sulfonic acid-(3) EXAMPLE 2 pound which has separated as a yellow precipitate is neutralized by the addition of sodium bi= 'i carbonate and introduced in portions at -5 G. into a solution of 21.8 parts of the sodium salt of 2-aminonaphthalene-3-carboxylic acid i'n'120 parts of Water. The whole is stirred for 3 hours whilst cooling with ice, after which the reaction mixture no longer gives the diazo reaction; The

Whole is then allowed to warm to room temperature and precipitation of the dyestuff is completed by the addition of common salt. After filtering by suction and drying the dyestufi constitutes a red-brown powder which dissolves in concentrated sulfuric acid yielding a violet-red coloration. It dyes wool in an acid bath yellowish-red shades which become grass green when after-chromed. It is also excellently suited for dyeing according to V the one-bath chroming process.

Instead of 2-amino-1-hydroxybenzene-sulfonic acid-(4) -anilide-carboxylic acid-(2) there may also be used 2-amino-l-hydroxybenzene-sulfonic acid- (4) -N-methyl'-N (,B-sulfo) -ethylamide or 2- amin'o-1-hydroXybenzene-sulfonic acid-(4) -'benz'ylamide-sulfonic acid- (4') The dyestuffs thus obtained possess similar properties.

boxylic acid of melting point 153 C. which is reduced according to one of the usual methods to 2 aminlo 1-hydr0xybenzene-sulfonic-acid- (4) methyleneamide-carboxylic acid.

Z-amino-l -hydrowybenzene-sulfonic-acid- (4) anilidecarboxylic-acid- (3 1 chloro 2 -nitrobenzene-sulfonic-acid-chloride-(4) is introduced by portions in the course of 1-2 hours at 40-50 C. into a solution of the equivalent quantity of the sodium salt of laminobenzene-carboxylic-acid-(3), the reaction being maintained neutral to weakly alkaline to litmus throughout by periodic addition of sodium carbonate. The condensation product is heated with the calculated quantity of dilute caustic I soda solution to boiling and the nitrophenol so obtained is reduced by means of sodium sulphide.

If 1 monoethyl-aminobenzene-sulfonic-acid- (4) l-monomethyl-aminobenzene-sulfonic acid- (4) or 1-monoethyl-arninobenzene-su1onic acid- (3) is used instead of l-aminobenzene-carboxylic acid-(3) the analogous products can be obtained according to the same process.

5 -chloro-2-amino-i -hydroxybenzene-sulfonicacid- (4) -ethyZanilide-sulfonic acid- (3) TABLE Composition of further dyestufis with Z-aminonaphthalene 3 carboxylic acid as coupling component I v colorofsomflon Shade ot'the dyeingonwool Example Diem-component inconcentrated Acid After-chromed 3 2-amgno i hydaoxybenzene-sulfonlcacid-(4)-metl1ylene-amide- Violet-red Reddish-orange Yellowis'hgreen. car oxyicaci a l 4 2-an1&no;l-hydtoxybenzene-su1fon c ac1d-(4)-an111d -carboxy11c do Yel1cwish-red Grass-green.

5 Z-amno- 1-hydroxybenzene-sulfonicacid-(4)-ethyT -ni1ide-Su1f0nic .do .jdo Bluish-green.

aci 4 6 2-aminog-%1y;lroxybenzene-sulfonic acid-(4)-methyl-anilide-su1i0- do .do Do.

nic-sci 4 7 2-amiimzghydroxybenzene-sulfonicacid-(4)-ethY1-ani1ide-Su1f0nic ..do do Do.

s 5-ch )ro:2-an%n5%-hydroxybenzenersulfonic acid-(4)-ethylanilide- .--.d0 Red Grass-green.

Sll 01110 861 9 5-niiiitp-Z-amiauz-lihydroxybenzene-sulfonic acid-(4)-ethylanilide- Bluish-red Bluish-red Olive-green.

su onic aci 4 1 0 6-nitrc-2-amino-1-hydroxybenzene-sulfonic acid(4)-ethy1-ani1idedo do Do.

sulfonic-acid-(4'). t

11 2-aminzi lihydroxybenzene-sulfonlcacid-(5)-ethylfl111l1de-su1f0n10 V1olet-red Red Grass-green.

- acid- 12 2-amnzi-;.-hydroxybenzene-sulfonic acid-(5)-anilide-carboxylic do ..do.- Dc.

aci 2' The'new 2-aminophenol derivatives used in responding ortho-nitrophenol by treatment with the calculated quantity of custic soda solution and the nitrophenol obtained is reduced according to the method of Bchamp.

5-mtro-2ammo-1 hydromybenzene-sulfonic} acid- (4) -ethylanilide-sulfonic acid- (4 2-amino-l-hydroxybenzene-sulfonic acid- (4) ethylanilide sulfonic acid-i4) is treated withphos'gene'in presence of caustic soda solution whilst cooling with ice until a free amino group can no longer'be detected; the benzoxazole sulfonic acid- -ethylanilide-sulfonic-acid- (4') thus formed is nitrated and the benzoxazole ring is again saponified by heating with an alkali solution to boiling. v r

6-nitro-2-amino-1-hydroxybenzene-sulfonic acid- (4) -ethylanilide-suZjonic-acid- (4) 2-amino-1-o:rybenzene-sulfonic-acid- (5) ethyZaniZide-sulfom'c-acid-(4') Benzoxazolone is converted into benzoxazolone sulfonic acid chloride-(6) by treatment with chloro-sulfonic acid at a moderate temperature, the resulting acid chloride is caused to react in the manner above indicated with l-aminoethylaminobenzene sulfonic acid (4) and the condensation product is deacylated by heating with an alkali solution.

The corresponding product is obtained by using l-aminobenzene carboxylic-acid-(iZ) instead of 1-amino-ethylaminobenzene-sulfonic-acid-(4) What we claim is:

1. Process for the manufacture of dyestufis which become green when chromed, consisting in coupling a diazotised 2-aminophenol, substituted in one of the positions 4 and 5 by a substituent containing a group imparting solubility in water selected from the group consisting of arylsulfone-radicals of the benzene series and sulfamide-radicals attached via the S02 group of the aliphatic series containing at most three carbon atoms and of the benzene series, with 2- aminonaphthalene-3-carboxylic acid.

2. The azodyestufis of the following general formula OH NH:

COOH

wherein one of the substituents X1 and X2 means a radical containing a group imparting solubility in water, selected from the group consisting of arylsulfone-radicals of the benzene series and sulfamide-radicals attached via the S02 group of the aliphatic series containing at most three carbon atoms and of the benzene series, the other of the substituents X1 and X2 being H and wherein Y means one of the group consisting of H, Cl and N02 being red to red-brown powders, dissolving in concentrated sulfuric acid with bluish-red to violet-red color and dyeing wool in an acid bath orange to red shades which, when after-chromed, turn to green shades of excellent fastness properties.

3. The azodyestuffs of the following general formula NH: COOH wherein X means a radical'containing group imparting solubility in water, selected from the group consisting of arylsulfone-radicals of the benzene series and sulfamide-radicals attached via the S02 group of the aliphatic series containing at most three carbon atoms and of the benzene series, being red to red-brown powders, dissolving in concentrated sulfuric acid with bluish-red to violet-red color and dyeing wool in an acid bath orange to red shades which, when after-chromed, turn to green shades of excellent fastness properties.

4. The azodyestufis of the formula following general NH: COOH wherein Z means one of the group consisting of H, CH3 and CzHs and V means one of the group consisting of COOH and SOsI-I, being red to redbrown powders, dissolving in concentrated sulfuric acid with bluish-red to violet-red color and dyeing wool in an acid bath orange to red shades which, when after-chromed, turn to green shades of excellent fastness properties.

5. The azodyestufi of the formula OH NHz COOH being a rust-red powder, soluble in concentrated sulfuric acid to a violet-red solution, dyeing wool in an acid bath yellowish-red shades which, when after-chromed, turn to bluish-green shades of excellent fastness properties.

6. The azodyestuif of the formula OH NH: 00011 I SlOa NH COOH being a red-brown powder, soluble in concentrated sulfuric acid to a violet-red solution, dyeing wool in an acid bath yellowish-red shades, which, when after-chromed, turn to grass-green shades of excellent fastness properties,

7. The azodyestufi" of the formula. N111 c0011 being a red powder, soluble in concentrated sulfuric acid to a. violet red solution, dyeing wool in an acid bath yellowish-red shades which, when after-chromed, turn to bluish-green shades of 5 excellent fastness properties.

A E- E CQNZET GUID'O SCi-IE'I'I'Y. 

